Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
  • C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
  • C23C22/08—Orthophosphates
  • C23C22/12—Orthophosphates containing zinc cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
  • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12771—Transition metal-base component
  • Y10T428/12785—Group IIB metal-base component
  • Y10T428/12792—Zn-base component
  • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

• the present invention relates to the field of phosphating for the anticorrosive pretreatment of zinc surfaces, wherein the use of largely nickel and cobalt-free Zinkphosphatierniesen is targeted.
• the present invention provides an alternative to trication zinc phosphating, in which the zinc surfaces of a component are first passivated with an alkaline composition containing iron (III) ions prior to zinc phosphating and thus preconditioned for largely nickel- and cobalt-free zinc phosphating.
• the invention relates to a component, in particular an automobile body, which at least partially has surfaces of zinc, wherein the zinc surfaces of a two-layer system consisting of a first inner, resting on the zinc surface passive layer containing iron and a second outer, on the inner layer overlying crystalline zinc phosphate layer are covered.
• the phosphatization of metals with a zinc-containing phosphating solution aims to produce solid metal phosphate layers on the metal surface which in themselves improve corrosion resistance and, in combination with paints and other organic coatings, substantially increase paint adhesion and resistance to corrosion undercutting ,
• Such phosphating processes have been known for a long time.
• the low-zinc phosphating in which the phosphating relatively low levels of zinc ions of z. B. 0.5 to 2 g / L have.
• An important parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually in the range of> 8 and can assume values of up to 30.
• the trication zinc phosphating provides the advantage that both zinc and iron or steel and aluminum can be provided with an excellent Lackhaftgrund with a crystalline zinc phosphate layer comparable quality, which form an excellent Lackhaftground for subsequently applied dip coatings.
• the layer-forming phosphating ie the provision of homogeneous crystalline coating coatings of zinc phosphate on steel, galvanized steel and aluminum, the trication-Zinkphosphat ist in terms of the achieved quality of the coatings so far unrivaled.
• the DE 19834796 and DE 19705701 disclose a process using low-nickel zinc phosphating which requires targeted post-passivation with lithium, copper or silver ions to achieve good corrosion protection on a metal mix of steel, galvanized steel and aluminum.
• the DE 4341041 discloses a nickel-free, low-zinc phosphating process, which focuses on the use of m-nitrobenzenesulfonate as an accelerator and a relatively low nitrate content of less than 0.5 g / L to obtain good corrosion protection results even on zinc surfaces.
• the DE 19606017 also discloses a low-zinc phosphating process free of nickel in which the phosphating solution contains copper ions to improve corrosion protection.
• a component which at least partially has surfaces of zinc or zinc alloys comprises within the meaning of the present invention both a semi-finished product made of zinc or galvanized steel, for example galvanized steel strip, and makes of same or different materials, for example an automobile body made of galvanized steel , Steel and aluminum.
• zinc alloy alloys with an impurity content of less than 50 at .-% understood.
• the term "zinc” includes both pure zinc and zinc alloys.
• Under rinsing step according to the invention is the flushing with city water or deionized water ( ⁇ ⁇ 1 ⁇ Scm -1 ) understood to remove water-soluble residues and particles from the component to be treated, which are abducted from a previous treatment step as adhering to the component.
• city water or deionized water ⁇ ⁇ 1 ⁇ Scm -1
• Activation according to the invention is understood to mean an activation of at least the zinc surfaces of the component for the subsequent phosphating, which supports the formation of uniform fine-crystalline zinc phosphate layers.
• the activation which is carried out according to the invention immediately before step ii) but after step i) is carried out with an aqueous composition which has a pH in the range of 3.5-13.
• the presence of an activation between step i) and step ii) is preferred according to the invention.
• Such activations and the associated activation baths are well known to those skilled in the phosphating and, for example, in the EP 1368508 disclosed.
• a parameter which is decisive for the effectiveness of the compositions (A) in step i) of the process according to the invention is the free alkalinity.
• the free alkalinity is determined by titrating 2 ml of bath solution, preferably diluted to 50 ml, with a 0.1 N acid such as hydrochloric acid or sulfuric acid to a pH of 8.5. The consumption of acid solution in ml indicates the score of free alkalinity.
• condensed phosphates in step i) of the process according to the invention are the water-soluble metaphosphates (Me n [P n O 3n ]), di-tri- and polyphosphates (Me n + 2 [P n O 3n + 1 ] or Me n [H z P n O 3n + 1 ]), the isometaphosphates and the cross-linked polyphosphates, where Me are either alkali metal or alkaline earth metal atoms.
• the corresponding condensed acids of the phosphoric acid may be used for the formulation of the compositions (A), provided that the free alkalinity is set as indicated.
• the mass-related proportion of the "condensed phosphates" according to component c2) in step i) of the process according to the invention is always calculated as a corresponding amount of PO 4 .
• this amount of condensed phosphates is always based on the equivalent amount of PO 4 .
• step ii) zinc phosphate layers on the zinc surfaces of the component are provided which form a corrosion-resistant lacquer adhesion base is completely equivalent to the paint adhesion base produced in a classical trication zinc phosphating.
• an aqueous alkaline composition (A) in step i) of the process according to the invention brings about a suitable passivation of zinc surfaces, which affords good bonding of the subsequent zinc phosphating, if the free alkalinity has less than 5 points. This is especially true for the application of the composition (A) in spraying, which causes a suitable passivation, especially when the free alkalinity is less than 4 points.
• compositions (A) in the Step i) may not have a high free alkalinity.
• the free alkalinity should preferably be at least 2 points in order to achieve optimal layer coverage on zinc surfaces of at least 20 mg / m 2 to produce iron based on the element.
• compositions (A) which have a free alkalinity above 6 points give rise to high iron coatings on the zinc surfaces, the adhesion to coating layers applied after step ii) is markedly reduced by high layer coverages relative to the element iron, so that Also, the corrosion protection is less effective or insufficient.
• the composition (A) in step i) of the process according to the invention has a pH of at least 10.5. Below a pH of 10.5, no layer deposits of iron of at least 20 mg / m 2 are formed on the zinc surfaces upon contacting them with a composition (A), so that for such low pHs, no alkaline Passivation of zinc surfaces for subsequent zinc phosphating takes place. In order to minimize the pickling attack on the zinc surfaces of the component, it is further preferred that the pH in the composition (A) in step i) of the method according to the invention is not above 13.
• the component also has surfaces of aluminum in addition to the surfaces of zinc
• the pH in the composition (A) in step i) of the method according to the invention does not reach values above 11.5, since otherwise the intensified pickling attack causes intensive black discoloration of the aluminum surfaces, the so-called “fountain black", which adversely affects the effectiveness of a subsequent conversion treatment, for example on the zinc phosphating in step ii) of the process according to the invention or in the case of aluminum phosphating discontinuous zinc phosphating in step ii) an acid subsequent passivation following the process according to the invention based on water-soluble inorganic compounds of the elements zirconium and / or titanium.
• the proportion of iron (III) ions in the composition (A) in step i) of the method according to the invention is preferably not more than 2000 mg / L. Higher proportions of iron (III) ions are unfavorable for the process, since the solubility of iron (III) ions in the alkaline medium must be maintained by correspondingly high proportions of complexing agent without more favorable properties in terms of the alkaline passivation of the zinc surfaces become.
• compositions (A) in step i) of the process according to the invention in which the proportion of iron (III) ions is at least 100 mg / L, more preferably at least 200 mg / L, on the one hand on the zinc surfaces in step i ) of the process according to the invention to ensure an alkaline passivation within typical procedural treatment times of less than two minutes and on the other hand to obtain in step ii) of the process according to the invention phosphate coatings in excellent layer quality.
• the complexing agents according to component c) of the alkaline composition (A) in step i) of the process according to the invention are preferably contained in such an amount that the molar ratio of all components c) to iron (III) ions is greater than 1: 1 and especially preferably at least 2: 1, more preferably at least 5. It turns out that the use of the amount of complexing agents in the stoichiometric excess is advantageous for the process, since in this way the proportion of iron (III) ions is kept permanently in solution. The precipitation insoluble Iron hydroxides are completely suppressed in this way, so that the composition (A) remains permanently stable and does not deplete of iron (III) ions.
• the composition (A) may additionally contain at least 100 mg / L of phosphate ions in step i) of the process according to the invention.
• This proportion of phosphate ions requires that, in addition to the iron ions, phosphate ions also constitute an essential constituent of the passivation layer produced on the zinc surfaces in step i). It has been found that such passive layers are advantageous for the subsequent zinc phosphating and, in conjunction with zinc phosphating, impart good adhesion to subsequently applied lacquer layers. Accordingly, it is further preferred in step i) of the process according to the invention that the compositions (A) contain at least 200 mg / L, more preferably at least 500 mg / L, of phosphate ions.
• the properties of the passive layer which is formed when the zinc surface of the component is brought into contact with compositions (A) in step i) of the process according to the invention, are not further positively influenced above a proportion of phosphate ions of 4 g / l, cf. that, for reasons of economy, the proportion of phosphate ions in the composition (A) in step i) of the process according to the invention should preferably be below 10 g / l.
• the ratio of iron (III) ions to phosphate ions can be varied within a wide range.
• the mass-related ratio of iron (III) ions to phosphate ions in a composition (A) in step i) of the process according to the invention is preferably in the range from 1:20 to 1: 2, particularly preferably in the range from 1:10 to 1: 3.
• Condensed phosphates are capable of holding iron (III) ions in solution in an alkaline medium by complexation. Although there are no particular restrictions on the nature of the condensed phosphates with regard to their usability for compositions (A) in step i) of the process according to the invention, preference is given to condensed phosphates selected from pyrophosphates, tripolyphosphates and / or polyphosphates, more preferably from pyrophosphates, because they are particularly soluble in water and very easily accessible.
• Lower acid numbers give the organic compounds surface-active properties, so that organic compounds c1) with acid numbers below 250 can act as anionic surfactants strongly emulsifying.
• the organic compounds are not high molecular weight and do not exceed a number average molecular weight of 5,000 ⁇ , more preferably 1,000 ⁇ .
• the emulsifying effect of the organic compounds c1) can be so pronounced when the preferred acid number and optionally the preferred molecular weight are exceeded, that contaminants introduced from the purification stage via the component in the form of oils and drawing fats can only be removed from the alkaline passivation stage via expensive separation processes , For example, by a dosage of cationic surfactants, so that further process parameters are controlled. It is therefore more advantageous to adjust the alkaline passivation step and thus the composition (A) in step i) of the process according to the invention only slightly emulsifying in order to allow a conventional separation of the floating oils and fats. Anionic surfactants are also prone to pronounced foam formation, which is particularly disadvantageous for example in the spray application of the composition (A).
• step i) of the process according to the invention preference is given to using organic complexing agents c1) having acid numbers of at least 250 in the composition.
• the acid number indicates the amount of potassium hydroxide in milligrams, which is required to neutralize 1 g of the organic compound c1) in 100 g of water according to DIN EN ISO 2114.
• Preferred organic complexing agents c1) in the composition (A) in step i) of the process according to the invention are selected from ⁇ -, ⁇ - and / or ⁇ -hydroxycarboxylic acids, hydroxyethane-1,1-diphosphonic acid, [(2-hydroxyethyl) (phosphonomethyl ) amino] -methylphosphonic acid, diethylenetriaminepentakis (methylenephosphonic acid) and / or amino-tris (methylenephosphonic acid) and salts thereof, more preferably hydroxyethane-1,1-diphosphonic acid, [(2-hydroxyethyl) (phosphonomethyl) amino] -methylphosphonic acid, diethylenetriaminepentakis (methylenephosphonic acid ) and / or amino tris (methylene phosphonic acid) and salts thereof.
• compositions (A) in step i) of the process according to the invention are explicitly included which contain exclusively condensed phosphates c2), exclusively organic complexing agents c1) or a mixture of both.
• the proportion of organic complexing agent c1) in the composition (A) can be reduced to the extent that complexing agent c2) selected from condensed phosphates is contained.
• both complexing agents c2) selected from condensed phosphates and organic complexing agents c1), wherein the molar ratio of all components c) to iron (III) ions greater as 1: 1, but the molar ratio of components c1) to ferric ions is less than 1: 1, more preferably less than 3: 4, but preferably at least 1: 5.
• a mix of both complexing agents c1) and c2) is advantageous in that the condensed phosphates in the alkaline medium at elevated temperature with the phosphate ions of the composition (A) are in equilibrium, so that by layer formation on the zinc surfaces spent phosphate ions from the condensed phosphates be replicated slowly.
• the presence of condensed phosphates alone is not sufficient to cause an alkaline passivation layer containing iron and phosphate on the zinc surfaces, so that the proportion of phosphate ions in the composition (A) in step i) of the method according to the invention is obligatory.
• compositions (A) are a mixture of complexing agents contained in step i) of the method according to the invention are preferred, wherein it should preferably be ensured that the molar ratio of components c1) to iron (III) ions is at least 1: 5.
• the composition (A) in step i) of the process according to the invention may additionally comprise nonionic surfactants.
• This additional purification and activation of the metal surfaces by means of compositions (A) containing nonionic surfactants affords the advantage that the passive layer formation on the zinc surfaces is more homogeneous compared to compositions (A) which do not contain nonionic surfactants as surface-active substances.
• a passivation formed homogeneously on the zinc surfaces of the component is a basic prerequisite for a likewise homogeneous formation of the zinc phosphate layer in step ii) of the method according to the invention.
• the nonionic surfactants are preferably selected from one or more ethoxylated and / or propoxylated C 10 -C 18 fatty alcohols having a total of at least two but not more than 12 alkoxy groups, more preferably ethoxy and / or propoxy, some with an alkyl radical, more preferably with a Methyl, ethyl, propyl, butyl radical may be end-group-capped.
• the proportion of nonionic surfactants in a composition (A) is preferably at least 10 mg / L, more preferably at least 100 mg / L, for sufficient purification and activation of the metal surfaces in step i) of the process according to the invention, and for economic reasons preferably not more than 10 g / L of nonionic surfactants are included.
• the use of highly emulsifying anionic surfactants should be avoided in the composition (A) for the reasons already explained above, so that their proportion of the composition (A) preferably not above 500 mg / L, more preferably not above 100 mg / L lies.
• a further advantage of the alkaline passivation with compositions (A) in step i) of the process according to the invention is that it is entirely possible to dispense with additions of heavy metal ions which are used in conventional alkaline compositions for passivation of zinc surfaces, so that the composition (A) preferably does not contain heavy metals selected from nickel, cobalt, manganese, molybdenum, chromium and / or cerium.
• the presence of small amounts of these heavy metals in the composition (A) used in a passivation step in the operation of a pretreatment line can not be completely avoided.
• nickel and manganese are common alloying constituents of steel which, when treated with the composition (A) in step i) of the process according to the invention, can pass through the partial dissolution of native oxide layers into the passivation step.
• the composition (A) in step i) of the process according to the invention therefore preferably contains a total of less than 10 mg / L of ionic compounds of the metals nickel, cobalt, manganese, molybdenum, chromium and / or cerium, in particular in each case less than 1 mg / L ionic compounds of the metals nickel and cobalt in each case based on the metallic element.
• the pickling of the zinc surfaces of the metallic component during the alkaline passivation in step i) of the method according to the invention causes zinc ions to enter the aqueous composition (A).
• This also applies to aluminum ions insofar as metallic components are treated which, in addition to the zinc surfaces, also have surfaces of aluminum.
• Metal cations of the elements zinc and aluminum have no negative impact on the effectiveness of the compositions (A) and are therefore tolerable.
• the component in step i) for at least 30 seconds, but not more than 4 minutes at a temperature of at least 30 ° C, more preferably at least 40 ° C, but not more than 70 ° C, especially preferably not more than 60 ° C is brought into contact with the alkaline aqueous composition (A).
• the compositions (A) cause, as already described, a passivation of the zinc surfaces of the component, which allows the growth of a crystalline, homogeneous and well-adherent zinc phosphate layer.
• the formation of the passive layer takes place thereby self-limiting, ie that depending on the specific formulation of the composition (A) certain maximum layer conditions can be realized.
• the preferred treatment or contact times should be selected in step i) of the method according to the invention so that the layer of iron is at least 20 mg / m 2 .
• the treatment and contact times for the realization of such a minimum layer coverage vary depending on the type of application and depend in particular on the flow of the aqueous fluids acting on the metal surface to be treated. Thus, the formation of passivation in processes where the composition is applied by spraying is faster than in dipping applications. Regardless of the type of application, the coating compositions (A) do not produce any layer deposits of iron significantly above 250 mg / m 2 due to the self-limiting passive layer structure.
• contacting the compositions (A) in step i) with the component having at least partial surfaces of zinc should immediately follow the alkaline passivation with or without subsequent rinsing step layer coatings of iron of at least 20 mg / m 2 , but preferably not more than 150 mg / m 2 realized realized.
• layer coatings of iron of at least 20 mg / m 2 , but preferably not more than 150 mg / m 2 realized realized.
• a deterioration of the adhesion-promoting properties of the deposited on the zinc surfaces in step ii) phosphate layers may already occur.
• the process according to the invention is of particular industrial importance, especially in the pretreatment of automobile bodies, since the alkaline passivation in step i) of the process according to the invention for the alkaline cleaning of the bodywork is effected directly, i. without intervening rinsing step, can follow. If the composition (A) in step i) of the process according to the invention additionally contains nonionic surfactants in a preferred embodiment, then the alkaline cleaning of the component or the body and the alkaline passivation of the zinc surfaces of the component can take place in one step. A separation of alkaline cleaning and alkaline passivation stage by a rinsing step is therefore just as little required as the performance of cleaning and alkaline passivation in two process steps and different baths.
• a method according to the invention is characterized in particular by the fact that the component which has at least partial surfaces of zinc is first brought into contact with an alkaline cleaner in a cleaning and degreasing bath, the alkaline cleaner preferably having a pH in the range from 9-14 without prior to subsequent contacting with the alkaline aqueous composition (A) in step i), a rinsing step.
• step i) an inorganic passivation layer containing iron is produced on the zinc surfaces, whereas on the other metallic surfaces of the component, which may be, for example, surfaces of iron, steel and / or aluminum, no deposition such an inorganic layer could be detected.
• step ii) of the process according to the invention wherein the composition (B) for zinc phosphating no water-soluble nickel and / or cobalt salts must be added , Accordingly, the process according to the invention replaces the usual in the automotive industry Trications Zinkphosphat réelle containing significant amounts of the heavy metals nickel and / or cobalt.
• composition (B) for zinc phosphating in step ii) of the process according to the invention is preferably not added at all to any nickel and cobalt ionic compounds.
• nickel ions are introduced into the phosphating solution.
• the amount of ionic compounds of the metals nickel and cobalt in the compositions (B) for zinc phosphating is preferably below 10 mg / L, more preferably below 1 mg / L, respectively the metallic element lies.
• the composition (B) For the phosphating of the zinc surfaces of the component in step ii), it is not absolutely necessary for the composition (B) to contain so-called accelerators. However, if components are treated which additionally have steel or iron surfaces, then it is necessary for their sufficient zinc phosphating in step ii) that the composition (B) contains one or more accelerators.
• accelerators are well known in the art as components of zinc phosphating baths. This is understood to mean substances which chemically bind the hydrogen formed by the pickling attack of the acid on the metal surface by being themselves reduced.
• At least nitrate ions are contained as an accelerator in an amount of not more than 2 g / L.
• the presence of manganese is particularly preferred.
• the possibility of the presence of divalent iron depends on the accelerator system described above.
• the presence of iron (II) in the stated concentration range requires an accelerator which does not oxidize towards these ions. Hydroxylamine should be mentioned as an example for this purpose.
• the manganese content of the composition (B) is preferably between 0.2 and 4 g / L, since at lower manganese contents, the positive influence on the corrosion behavior of the phosphate layers is no longer present and no further positive effect occurs at higher manganese contents. Contents between 0.3 and 2 g / l and in particular between 0.5 and 1.5 g / l in the composition (B) in step ii) of the process according to the invention are particularly preferred.
• the zinc content of the composition (B) in step ii) of the process according to the invention is preferably adjusted to values between 0.45 and 2 g / l.
• the actual zinc content of the composition (B) increases up to 3 g / L.
• the form in which the zinc and manganese ions are introduced into the composition (B) is of no importance in principle. It is particularly appropriate to use as the source of zinc and / or manganese, the oxides and / or carbonates.
• the compositions (B) in step ii) of the process according to the invention additionally comprise copper (II) ions in the range from 1 to 30 mg / L, if the component to be treated according to the invention also contains, in addition to the surfaces of zinc, surfaces of iron or metal Steel in order to promote the formation of particularly advantageous zinc phosphate layers on the surfaces of iron or steel in step ii).
• the component to be treated according to the invention is not also composed of surfaces of iron or steel, the addition of copper (II) ions can be dispensed with in step ii) since such an additive does not affect the properties of the zinc phosphate layer on the other metal surfaces positively influenced.
• the composition (B) in step ii) of the process according to the invention contains less than 0.01 g / L, more preferably less than 0.001 g / L of copper (II) ions.
• the weight ratio of phosphate ions to zinc ions in the composition (B) in step ii) of the process according to the invention can vary within wide limits and is preferably in the range between 3.7 and 30, more preferably in the range between 8 and 20.
• the known fact is disregarded that at the pH values of the composition (B) for zinc phosphating, only a very small part of the phosphate is actually in the form of the triply negatively charged anions. Rather, at these pH levels, the phosphate is expected to exist primarily as a single dihydrogen phosphate anion with a slight negative charge, along with lesser amounts of undisociated phosphoric acid and doubly negatively charged hydrogen phosphate anions.
• composition (B) Another important parameter for the composition (B) is its content of free acid and total acid.
• Free acid and total acid represent an important control parameter for phosphating baths since they represent a measure of the pickling attack of the acid and the buffering capacity of the treatment solution and have a correspondingly great influence on the achievable coating weight.
• the term free acid is well known to those skilled in the phosphating art. The method of determination specific for this invention for determining the free acid or total acid content in a composition (B) is given in the examples section.
• composition (B) in step ii) has a free acid content, each staggered according to increasing preference, of at least 0; 0.2; 0.4; 0.6; 0.8; 1 point, but not more than 3; 2.5; 2; 1.5 points.
• the total acid content of the composition (B) in step ii) of the process according to the invention is staggered in each case corresponding to an increasing preference at least 20; 21; 22 points, however, not more than 30; 28; 26; 25; 24 points.
• the pH of the aqueous treatment solution is preferably not less than 2.2 with increasing preference. 2.4; 2.6; 2.8 but not greater than 3.6; 3.5; 3.4; 3.3; 3.2.
• the component to be treated is a composite metal construction which, in addition to the surfaces of zinc, also has surfaces of iron, steel and / or aluminum, and if a zinc phosphate layer is to be formed on all metal surfaces in step ii), it is advantageous to use the Composition (B) to add water-soluble inorganic compounds which are a source of fluoride ions.
• the addition of free and / or complexed fluoride to a composition (B) is preferably carried out in amounts of up to 2.5 g / l of total fluoride, of which up to 300 mg / l of free fluoride. Due to the presence of the fluoride ions, the pickling rate on the metal surfaces is increased, but the aluminum ions produced during the treatment of aluminum surface components are directly complexed so that inhibition of zinc phosphating on the metal surfaces of the component can be prevented.
• the aluminum content in the composition (B) should not exceed 3 mg / L.
• higher Al contents are tolerated due to complex formation unless the concentration of uncomplexed aluminum ions exceeds 3 mg / L.
• the Use of fluoride-containing compositions (B) in step ii) of the process according to the invention is therefore advantageous if the metal surfaces of the component to be phosphated consist at least partially of aluminum or contain aluminum. In these cases, it is favorable to use no complex-bound, but only free fluoride, preferably in concentrations in the range 0.1 to 0.3 g / L.
• free fluoride is well known to those skilled in the phosphating art.
• the determination method for determining the free fluoride content in a composition (B) specific to this invention is given in the examples section.
• the composition (B) for zinc phosphating may additionally comprise silicon in the form of water-soluble inorganic compounds, preferably in the form of fluorocomplexes of silicon, more preferably in the form of Hexafluorosilicic acid and / or salts thereof.
• silicon in the form of water-soluble inorganic compounds preferably in the form of fluorocomplexes of silicon, more preferably in the form of Hexafluorosilicic acid and / or salts thereof.
• Such point defects in the phosphating can be the starting point for the corrosive delamination of subsequently applied organic coating systems, so that the occurrence of specks in practice is largely to be avoided.
• the optional addition of water-soluble inorganic compounds of silicon to a composition (B) in step ii) of the method according to the invention prevents the formation of specks in a subsequent coating of the metal surfaces, for this purpose preferably at least 0.025 g / L of these compounds calculated as SiF 6 in the Composition (B) should be included and for reasons of economy of the method preferably not more than 1.5 g / L, more preferably not more than 1.0 g / L are included.
• Selective phosphating is understood according to the invention to mean that zinc zinc phosphate layers having a coating weight of at least 0.5 g / m 2 , preferably of at least 1 g / m 2 , but preferably not more than, are formed on the surfaces of zinc and possibly iron or steel 3.5 g / m 2 are deposited, while on the surfaces of aluminum no zinc phosphate layers are formed.
• step ii) The requirement that no zinc phosphate layer may form in this preferred embodiment of the method according to the invention on the aluminum surfaces of the component in step ii) is understood to mean that there is no closed and sealed crystalline layer, characterized in that the surface-related mass of The zinc phosphate deposited on the aluminum parts shall not exceed 0,5 g / m 2 .
• the coating of zinc phosphate is according to the present invention for all metal surfaces of the Component determined on test sheets or sections of the individual metallic materials of the component in composite construction.
• steel parts, galvanized or alloy-galvanized steel parts of the component immediately after step ii) of the inventive method for 15 minutes with an aqueous 5 wt .-% CrO 3 solution at a temperature of 70 ° C in contact and in this way of the Zinc phosphate layer freed.
• aluminum sheets are brought into contact with an aqueous 65% strength by weight HNO 3 solution at a temperature of 25 ° C. for 15 minutes immediately after a step ii) and are freed from zinc phosphate portions accordingly.
• the component in step ii) is to be brought into contact with a composition (B) for zinc phosphating which has a temperature in the range of 20-65 ° C and contains an amount of free fluoride (measured in g / L), which is not greater than the quotient of the number 8 and the solution temperature in ° C (8 / T).
• a composition (B) for zinc phosphating which has a temperature in the range of 20-65 ° C and contains an amount of free fluoride (measured in g / L), which is not greater than the quotient of the number 8 and the solution temperature in ° C (8 / T).
• crystalline zinc phosphate layers are also produced on the aluminum surfaces of the component.
• composition (B) additionally contains silicon in the form of water-soluble inorganic compounds in step ii) to prevent the formation of specks on the zinc surfaces of the component
• a selective zinc phosphating of the component consisting of zinc and aluminum it is preferred for a selective zinc phosphating of the component consisting of zinc and aluminum that the composition (B) is at least 0.025 g / L but less than 1 g / L of silicon in the form of water-soluble inorganic compounds calculated as SiF 6 and the product (Si / mM).
• step ii) the formation of zinc phosphate crystal nests on the aluminum surfaces of the component in step ii) is almost completely suppressed, so that after step ii) result in shiny metallic aluminum surfaces, which in a process according to the invention subsequent conversion treatment of the component, for example Acidic aqueous compositions containing water-soluble compounds of zirconium and / or titanium, passivate very well and thereby form a good paint adhesion base.
• the upper limit for the content of water-soluble inorganic compounds of silicon in composition (B) in step ii) according to this preferred embodiment is on the one hand due to the economy of the process and on the other hand due to the fact that the process control by such high concentrations of water-soluble inorganic compounds containing Silicon is much more difficult, since the formation of zinc phosphate crystal nests on the Aluminum surfaces can be pushed back on an increase in the free acid content only insufficient.
• the crystal nests typically represent local surface defects that may be the starting points for the corrosive delamination of a subsequently applied dip.
• the phosphating in step ii) of the process according to the invention can be carried out by spraying, dipping or spray-dipping.
• the exposure time or the period of contact with the composition (B) is in the usual range between about 30 seconds and about 4 minutes.
• the method according to the invention can also be carried out as a strip method on running galvanized steel strip.
• contact times with the respective compositions in steps i) and ii) in the range from about 2 to about 20 seconds are usual, wherein step ii) can also be carried out in so-called "no-rinse" application.
• step ii) can be followed in each case immediately by further rinsing steps with intervening rinsing steps, which are in particular selected from a post-passivation and / or a cathodic dip-coating.
• the present invention therefore furthermore relates to a component which has at least partial surfaces of zinc, in which the surfaces of zinc comprise a layer system comprising a first inner passive layer on the zinc surface containing iron and a second outer, lying on the inner layer of crystalline zinc phosphate layer wherein the support of the inner layer 20 to 150 mg / m 2 based on the element iron and the support of the outer zinc phosphate layer 0.5 to 3.5 g / m 2 , obtainable in a previously described inventive method.
• the first inner layer of the component according to the invention which is produced in step i) of the method according to the invention, contains the element iron in oxidized form.
• the first inner layer on the zinc surfaces of the component then contains phosphate ions when the component has previously been brought into contact with a composition (A) in a preferred process according to the invention in step i) which additionally contains at least 100 mg / L of phosphate ions contains.
• the second outer layer on the zinc surfaces of the component which is a zinc phosphate layer, in each case contains less than 10 mg / m 2 of nickel and cobalt.
• the detection of the first inner layer on the zinc surfaces of the component according to the invention succeeds after removal of the second outer layer, which is a zinc phosphate layer, with chromic acid, wherein the coating layer of iron in the first inner layer on the zinc surfaces of the component according to the invention is determined by means of a UV spectroscopic analysis method described in the Examples section (see Table 1), while the chemical state of the element iron in the layer is determined by X-ray photoelectron electron spectroscopy ( XPS) is to be made.
• XPS X-ray photoelectron electron spectroscopy
• the detection of phosphate ions in the first inner layer on the zinc surfaces of the component preferred according to the invention can also be performed by X-ray photoelectron spectroscopy (XPS).
• the proportion of nickel or cobalt in the second outer layer of the preferred component according to the invention is quantified by ICP-OES in the pickling solution after detachment of the zinc phosphate layer from the zinc surfaces of the component and related to the pickled surface, so that a formal layer support based on these elements can be specified.
• the component according to the invention may have on its zinc surfaces further outer layers, which are preferably selected from organic paints.
• the component according to the invention represents an automobile body.
• the free acid score in the example baths E1-E5 according to a composition (B) is determined by diluting 10 ml bath sample to 50 ml and titrating with 0.1 N sodium hydroxide solution to pH 3.6. The consumption of ml of sodium hydroxide gives the score. Accordingly, the content of total acid is determined by titrating to a pH of 8.5.
• the content of free fluoride in the exemplary baths E1-E3 according to a composition (B) is detected by means of a potentiometric measuring chain (Fa. WTW, inoLab ®, pH / IonLevel 3).
• the measuring chain contains a fluoride-sensitive glass electrode (WTW, F501) and a reference electrode (WTW, R503).
• WTW, F501 fluoride-sensitive glass electrode
• WTW, R503 reference electrode
• both electrodes are together successively in calibration solutions with a content of 100 mg / L and 1000 mg / L of free fluoride, prepared from the Titrisol ® fluoride standard of Fa. Merck without addition of buffer, dipped.
• the resulting measured values are corrected with the respective fluoride content "100" or "1000" and read into the measuring instrument.
• the slope of the glass electrode is then displayed in mV per decade of the fluoride ion content in mg / L on the meter, typically between -55 and -60 mV.
• the fluoride content in mg / L is then determined directly by immersing the two electrodes in the exemplary baths E1-E5 at a temperature of 25 ° C.
• Tab. 1 shows the influence of the alkaline passivation followed by a nickel-free or low-nickel zinc phosphating (Examples 1-4 and 5) on the adhesion of the cathodic dip to the zinc substrate after water storage and subsequent cross hatch test.
• the nickel-free zinc phosphating which takes place from a composition (B) with or without the addition of copper ions, but without alkaline passivation with a composition (A), on the galvanized substrate an insufficient paint adhesion (Examples 6, 7).
• the nickel-containing trication-phosphating (Example 8) - as known in the art - provides excellent adhesion of the coating composition to the substrate.
• adhesion that is completely equivalent to nickel-containing phosphating is achieved if the layer coating of iron after the alkaline passivation is moderate, ie, for example about 100 mg / m 2 based on the element iron (Examples 1, 3).
• the coating weight of zinc phosphate results from the multiplication of the area-related amount of phosphorus with the factor 6.23.
• the calibration was carried out in a two-point method by determining the absorption values of identical volumes (300 ⁇ l) of two standard solutions of ferric nitrate in 5% strength by weight nitric acid, which was used to determine the absorption values at 25 ° C. in the measuring cuvette containing 5 ml of a 1.0% sodium thiocyanate solution.

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